Methods and systems for the selective formation of thiourethane bonds and compounds formed therefrom

Abstract

The present techniques relate to thiourethane compositions formed by reacting a reactive composition containing active molecules having an average of at least one thiol group per active molecule and an average of at least one hydroxyl group per active molecule with a monomer composition containing monomer molecules having an average of at least two isocyanate groups per monomer molecule. The reactions are performed in the presence of an amine catalyst, which may preferentially react thiol groups over hydroxyl groups, thus forming a thiourethane composition having, on average, more hydroxyl groups than thiol groups and more thiourethane groups than urethane groups, on a normalized basis.

1 . A composition comprising the contact product of contact elements comprising:
 a reactive composition comprising active molecules having an average of at least one thiol group per active molecule, and an average of at least one hydroxyl group per active molecule, wherein each active molecule has at least one thiol group, or at least one hydroxyl group, or both;   a monomer composition comprising monomer molecules having an average of at least two isocyanate groups per monomer molecule; and   an amine catalyst;   wherein the contact product comprises molecules having a normalized average number of hydroxyl groups per molecule that is greater than a normalized average number of thiol groups per molecule, and wherein a normalized average number of thiourethane groups in the contact product is greater than a normalized average number of urethane groups.   
   
   
       2 . The polymer of  claim 1 , wherein a ratio of the normalized average number of hydroxyl groups per polymer molecule to the normalized average number of thiol groups per polymer molecules in the polymer is greater than about 2:1. 
   
   
       3 . The polymer of  claim 1 , wherein a ratio of the normalized average number of thiourethane groups per molecule to the normalized average number of urethane groups in the contact product is greater than about 2:1. 
   
   
       4 . The polymer of  claim 1 , wherein the reactive composition comprises active molecules formed from an unsaturated ester, the active molecules comprising a mercaptanized unsaturated ester, a mercaptanized epoxidized unsaturated ester, a crosslinked mercaptanized unsaturated ester, or a hydroxyl thiol ester, or any combination thereof. 
   
   
       5 . The polymer of  claim 4 , wherein the unsaturated ester comprises a tallow oil, an olive oil, a peanut oil, a castor bean oil, a sunflower oil, a sesame oil, a poppy seed oil, a palm oil, an almond seed oil, a hazelnut oil, a rapeseed oil, a canola oil, a soybean oil, a corn oil, a safflower oil, a cottonseed oil, a camelina oil, a flaxseed oil, or a walnut oil, or any combination thereof. 
   
   
       6 . The polymer of  claim 4 , wherein the unsaturated ester comprises a synthetic unsaturated ester. 
   
   
       7 . The polymer of  claim 1 , wherein the monomer molecules comprise aliphatic isocyanates having an average of at least two isocyanate groups per molecule, cycloaliphatic isocyanates having an average of at least two isocyanate groups per molecule, or aromatic isocyanates having an average of at least two isocyanate groups per molecule, or any combination thereof. 
   
   
       8 . A method for selectively forming thiourethane groups, comprising:
 forming a mixture comprising:
 a reactive composition comprising active molecules having an average of at least one thiol group per active molecule and an average of at least one hydroxyl group per active molecule; 
 a monomer composition comprising monomer molecules having an average of at least at least one isocyanate group per monomer molecule; and 
 an amine catalyst; and 
   allowing the mixture to react to form a final composition comprising molecules having a normalized average number of thiourethane groups per molecule that is greater than a normalized average number of urethane groups per molecule, and having a normalized average number of hydroxyl groups per molecule that is greater than a normalized average number of thiol groups per molecule.   
   
   
       9 . The method of  claim 8 , wherein a ratio of a number of isocyanate groups to the sum of the number of thiol groups and hydroxyl groups in the mixture is between about 0.1:1 and about 1:1. 
   
   
       10 . The method of  claim 8 , wherein a ratio of a number of isocyanate groups to the sum of the number of thiol groups and hydroxyl groups in the mixture is between about 0.1:1 and about 0.5:1. 
   
   
       11 . The method of  claim 8 , wherein a ratio of a number of isocyanate groups to the sum of the number of thiol groups and hydroxyl groups in the mixture is between about 0.1:1 and 0.25:1. 
   
   
       12 . The method of  claim 8 , wherein the final composition has a ratio of the normalized average number of hydroxyl groups to the normalized average number of thiol groups of greater than about 2:1. 
   
   
       13 . The method of  claim 8 , wherein a ratio of the normalized average number of thiourethane groups per molecule to the normalized average number of urethane groups per molecule in the mixture is greater than about 2:1. 
   
   
       14 . The method of  claim 8 , wherein forming the mixture comprises adding a solvent. 
   
   
       15 . The method of  claim 14 , wherein wherein the solvent comprises methyl ethyl ketone, glycerol carbonate, acetone, hexane, heptane, petroleum distillate, butyl acetate, toluene, or benzene, or any combination thereof. 
   
   
       16 . A composition comprising molecules having thiourethane groups and hydroxyl groups, wherin the molecules have a normalized average number of hydroxyl groups per molecule that is greater than a normalized average number of thiol groups per molecule. 
   
   
       17 . The composition of  claim 16 , wherein a ratio of the normalized average number of thiourethane groups per molecule to a normalized average number of urethane groups per molecule in the composition is greater than about 1:1. 
   
   
       18 . A formulation for a coating or adhesive, comprising:
 a first part comprising thiourethane molecules having thiourethane groups and hydroxyl groups, wherein a ratio of a number of hydroxyl groups per thiourethane molecule to a number of thiol groups per thiourethane molecule is greater than about 1:1; and   a second part comprising monomer molecules having an average of at least two reactive groups per monomer molecule, wherein the reactive groups can react with the hydroxyl groups to form bonds.   
   
   
       19 . The formulation of  claim 18 , wherein a ratio of the number of hydroxyl groups to the number of thiol groups in the compound is greater than about 2:1. 
   
   
       20 . The formulation of  claim 18 , comprising a catalyst composition comprising a metal catalyst, or an amine catalyst, or a combination thereof, wherein the catalyst composition is included in the first part, is included in the second part, or is provided as a third part, or any combination thereof. 
   
   
       21 . The formulation of  claim 18 , wherein the reactive groups comprise isocyanate groups. 
   
   
       22 . The formulation of  claim 18 , wherein the reactive groups comprise acid groups, acid anhydride groups, epoxy groups, phthalate groups, or isocyanate groups. 
   
   
       23 . The formulation of  claim 18 , wherein the first part, the second part, or both, comprise a solvent. 
   
   
       24 . The formulation of  claim 23 , wherein the solvent comprises methyl ethyl ketone, glycerol carbonate, acetone, hexene, petroleum distillate, butyl acetate, toluene, benzene, or any combination thereof. 
   
   
       25 . A method of making a formulation for a coating or adhesive, comprising:
 providing a first part comprising molecules having thiourethane groups and hydroxyl groups, wherein a normalized average number of hydroxyl groups per molecule is greater than a normalized average number of thiol groups per molecule; and   providing a second part comprising monomer molecules having an average of at least two reactive groups per monomer molecule, wherein the reactive groups can react with the hydroxyl groups to form bonds.   
   
   
       26 . The method of  claim 25 , comprising providing a catalyst composition comprising a metal catalyst, or an amine catalyst, or a combination thereof, wherein the catalyst composition is included in the first part, is included in the second part, or is provided as a third part, or any combination thereof. 
   
   
       27 . A formulation for a coating or adhesive, comprising:
 a first part comprising a compound having thiourethane groups and hydroxyl groups, wherein a normalized average number of hydroxyl groups is greater than a normalized average number of thiol groups; and   a second part comprising monomer molecules having an average of at least two reactive groups per monomer molecule, wherein the reactive groups can react with the hydroxyl groups to form bonds.